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Preparation of 1-C14-Propene-1 and the Mechanism of Permanganate Oxidation of Propene

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Preparation of 1-C14-Propene-1 and the Mechanism of Permanganate Oxidation of Propene Lawrence Berkeley National Laboratory Lawrence Berkeley National Laboratory Title Preparation of 1-C14-Propene-1 and the Mechanism of Permanganate Oxidation of Propene Permalink https://escholarship.org/uc/item/7t33m6zb Author Fries, B.A. Publication Date 2010-01-20 Peer reviewed eScholarship.org Powered by the California Digital Library University of California UCRL /9 ~7S'~ c\ \ UNIVERSITY OF CALIFORNIA NOT TO BE TAKEN FROM THIS ROOM I 1·<F;, h , . BERKELEY, CALIFORNIA ·. ENG-48 INDEX II 0 • UCRL 19 This document contai-n-s--·,.......2.,.O--p-g-.s'--;-'- and 0 plates of figureS:--- This is-Copy~of 76 • Series A I DO NOT Ii.E''[tOVE TUS PAGE Issued to: INFORMATION DIVISION ~ilitl~~;t;:_:,.;:.p',!~~:~"Cr ."~~-F' ~"""'i"'~-:~"~i'T<i:,;' \'d: .r'::··'\ [l· .. "-j ---rC lassificathJ~~:t~o f ~J~ Sta;,~!~d·>'h~~~f.; 'A 1. This .document contains restricted data withinClt~~SI~e~~g~LQt'itl;~.·AtgJ:i~Ut'N~1-''CV Act of :1,.946 and/or informu.tion affecting tho ndt"1artitF'ds1Censie>~fr,tlwcJJn,itl:l'd:'"" States within the meaning of the Espionage Act u. S. C. 31 & 32, as amended. Its transmission or the revelation of its contents in 8.n'-' manner to an un:J.utl-\'.)r~ il';ed perscm is prohibited'and may result in' severe crimi~,al penalty.:-----.----- 2. Before this dOClUTlentcan begiventoa person toread~ hiS name must be ..,n the Heading List of those authorized to read material on this subject, or permissic must be obtained from the Information Division or the £~ecutive Office. 3. A SECRET or CONFIDEHTIAL document is t.., be kept only in a guarded area. When stored, it inust be kept 'in a locked safe or in a loc;Ced filing Case with a tumb ler lock. 4. A SECRET or COnFID8HTIAL docUJaent is n~t to 1;6 copied or otherwise duplicated withr.mt permlss ion-of the c-riginatir.g---offue. 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Initial and date the pag:3s of' this document which c;escribe any work that you hav":J witn05sod; adJin,; any p8rtinent infor:nation, S~Jch as re:ferences to Or,1.g1n­ a1 work reoords .This docu,'11ent, properly signed, datc,d and anr- otated, is import­ ant in p~tent preparation. 8. Each person who r'J:,Gs this docu;!lent must sign this cover sheet '.:::elow. Please sign and date thv -'(;ov,::,r sheet ai'ferreaZli;gth8 'rGpC'lrt-;-X~') state by Yes or No whether or not n~tes have been taken. See paragraph 4 above. 1c'~,tes? Date Route to P.eac. by Netes? Date '--'- -.---- -.-.---1·--- .------.--'''., ...-------..---. I ...1l.o.....-..--j,-L;'-"-'--f-J..LLJ+'/UIr.rK --------j--.-.-----I .----.--I~- ~~ --·--1----------··-- -._- -----..-t----------.--------- ,----.----~----.--.- -.------ -------J-------------.--- -------~-----------.-.-- 1 ' --------------- .. -------. --- ~r--,-.------~--.---- ----- I I --+-----+---I~---]~-~------~~--~--.----~~ -~------.--~~- --.-- - .. -I --'----. -+.._L -I-- -' A·-l6 UNIVERS~TY OF CALIFORnIA RADIAT!ON LABORATORY Contract No. W-7405-Eng .-48 PREPARATION OF l-C14_PROPENE-1 AND THE MEQHANISM OF PERMANGANATE OXIDATION OF PROPENE by B. A. Fries and M. Calvin 10 December 1947 This document contains restricted data within the mean­ ing of the Atomic Energy Act of 1946 and/or information affecting the national defense of the United States within the meaning of the Espionage Act U.S.C. 31 & 32, as amended. Its transmission or the revelation of its contents in any manner to an unauthorized person is prohibited and may result in severe criminal penalty. Berkeley, California ,UCm. 19 " "j' X.~i ,' ..""," -'f t. , Chemistry-General -2- Standard Distribution UCRL 1~ Serie~/A: No. Copies.. / .- / ,) Argonne National Laboratory 10 Atomic Energy Commission 3 // _ /'3 Battelle Memorial Institute 1 /1-/ Brookhaven National Laboratory 10 /,;- ..2,1 Carbide & Carbon Chemicals Corp. (K-25 Area) 2 ::2 s·- .' ,;I (f' Carbide & Carbon Chemicals Corp. (Y-12 Area) 2 Clinton Laboratories 12 Io/C) f/ (/ General Electric Company 4 Hanford Engineer lrTorks 2 '-I .(;, ,c< Iowa State College 1 <-J 7 Los Alamos 3 Madison Square Area 1 Massachusetts Institute of Technology 1 Monsanto Chemical Company, Dnyton 1 _,ff' National Bureau of Standards 2 ,-S:"t'!.,Ji ",<, ••':..:3 Patent Advisor 1 Research Division (for NEPA), Ouk Ridge 1 Research Division, Ollie Ridge 15 University of California, Radiation Laboretory '73 Chemistry 1 W. M. Latimer 1 ") 'l .' I.~' ~ "I (" Information Division 2 f .~;) TOTAL ~ Radiation Laboratory University of California Berkeley, California -3- ~- UCRL-19 ABSTRACT PREPARATION OF l-C~4_PROP}<~HE-l AND THE MECHANISM OF P~RMANGANATE OXIDATION OF PROPENE by B. A. Fries and M. Calvin From the Radiation Laboratory and Department of Chemistry, University of California; Berkeley. 10 December 1947 ABSTRACT •. l-C14_propene~1 has been prepared. The migration of the double bond under a variety of experimental conditions in the preparation of propene has been investigated. 'rhe mechanism of the permanganate oxi- dation of the labelled propene has been examined; it has been found to proceed by several paths, the relative importance of which depends upon the experimental conditions .. especia lly the pH. Contract No. W-7405-eng-48. For pUblication in J. Am. Chem. Soc. UCRL-l9 PREPARATION OF l-C14_PROPENE-l AND THE MECHANISM OF PERMANGANATE OXIDATION OF PROPENE* by B••A Fr1es• ** an.d M Cal·V1n From the Radiation Laboratory and Department of Chemistry, University of California, Berkeley_ 10 December 1947 The preparation of l-C14_propene_l was undertaken in order to have available propene labelled in a terminal position and, incidently, to study the stability of the double bond when preparing propene under a variety of conditions. During the course of this investigation, a re- liable procedure for the degradative analysis of the propene had to be developed. This analytical problem led to a study of the oxidative degradation of propene with permanganate. A number of methods were available for the preparation of propene. Several of these methods were tried with 014 labelled materials, while others were discarded when preliminary tests with nonradioactive materials indicated either very poor yields or impure products. The first three • Our thanks are due to Mrs. Martha Kirk for her technical assistance in this work and particularly for the performance of many of the isotopic analyses. ** While on leave from California Research Corporation, Richmond, Cali­ fornia. -5- UCRL-19 It 11 of the following methods were actually en:ployed for radioaotive propene synthesis. 1) Dehydration of n-propanol with metaphosphoric acid 2) . Dehydration of n-propanol ov~r heated alumina 3) Pyrolysis of n-propyltrimethylammonium hydroxide 4) Pyrolysis of methyl n-propyl xanthate 5) Dehydrobromination of n-propyl bromide with alcoholic KOH Extensive rearrangement of the double bond was found to occur when pre- paring propene by dehydration with metaphosphoric acid and with heated A1 203 • However, the pyrolysis of the quaternary ammonium base gave little, if any, rearrangement and the product consisted principally of l4 c~\ l-C _propene-l (CH3-CH=tH2), wher-ea s in the other ses, mixtures of l-C14_proDene-l and 3-c14 _proDtme-l (~H3-CB=CH2) were obtained. Degradation Procedure The important features desired in the degradative process include. 1) minimum number of operations 2) easy separation of the products of the degradation reaction 3) unequivocal identification of the origin of these products. Here again several choices were available, among them, oxidative degrada- tion with permanganate and dichromate, ozonolysis, and glycol formation with hydrogen peroxide and subsequent oxidation and splitting of the glycol with periodate. Ozonolysis of propene gives rise to a mixture of formaldehyde and acetaldehyde, which are not too easily separated. Preliminary glycol formation and periodate oxidation also yields these same two aldehydes and in addition involves more manipulation. -6- UCRL-l9 ~manganate OXid~tion of ~!2pene. Acid permanganate oxidation should produce acetic and carbonic acids if propylene glycol is an intermedtate, This appeared to be a satisfactory procedure, particularly since Evans (1) reported that propylene glycol was converted quantitatively to acetic acid and CO 2 with neutral permanganate at 50 oC, although in the presence of alkali, oxalic acid was formed, Hence, examination of the acetic and carbonic aoids for 014 should indicate the extent of labelling of the two term- inal carbon atoms of the propene. Howe~er, rearrangement of the double bond might also occur dUring the analysis, but this could not be deter- mined until some radioactive propene had been prepared. Although per- manganate oxidation was chosen for the degradative analysis, in one instance ozonolysis was employed to confirm the results of the perman- ganate method. The following procedure was first tested with non-radioactive propene. Approximately three millimoles of propene was introduced into an evacuated 3-necked flask of about 385 mI. volume. Fifty mI. of water or buffer solution was added through a dropping funnel.
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